Bromination of Graphene and Graphite

We present a density functional theory study of low density bromination of graphene and graphite, finding significantly different behaviour in these two materials. On graphene we find a new Br2 form where the molecule sits perpendicular to the graphene sheet with an extremely strong molecular dipole. The resultant Br+-Br- has an empty pz-orbital located in the graphene electronic pi-cloud. Bromination opens a small (86meV) band gap and strongly dopes the graphene. In contrast, in graphite we find Br2 is most stable parallel to the carbon layers with a slightly weaker associated charge transfer and no molecular dipole. We identify a minimum stable Br2 concentration in graphite, finding low density bromination to be endothermic. Graphene may be a useful substrate for stabilising normally unstable transient molecular states

Optical Absorption and Raman Spectroscopy Study of the Fluorinated Double-Wall Carbon Nanotubes

Double-wall carbon nanotube (DWNT) samples have been fluorinated at room temperature with varied concentration of a fluorinating agent BrF3. Content of the products estimated from X-ray photoelectron data was equal to CF0.20 and CF0.29 in the case of deficit and excess of BrF3. Raman spectroscopy showed considerable decrease of carbon nanotube amount in the fluorinated samples. Analysis of optical absorption spectra measured for pristine and fluorinated DWNT samples revealed a selectivity of carbon nanotube fluorination. Nanotubes with large chiral angle are more inert to the fluorinating agent used

Electronic Structure of Nitrogen- and Phosphorus-Doped Graphenes Grown by Chemical Vapor Deposition Method

Heteroatom doping is a widely used method for the modification of the electronic and chemical properties of graphene. A low-pressure chemical vapor deposition technique (CVD) is used here to grow pure, nitrogen-doped and phosphorous-doped few-layer graphene films from methane, acetonitrile and methane-phosphine mixture, respectively. The electronic structure of the films transferred onto SiO2/Si wafers by wet etching of copper substrates is studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy using a synchrotron radiation source. Annealing in an ultra-high vacuum at ca. 773 K allows for the removal of impurities formed on the surface of films during the synthesis and transfer procedure and changes the chemical state of nitrogen in nitrogen-doped graphene. Core level XPS spectra detect a low n-type doping of graphene film when nitrogen or phosphorous atoms are incorporated in the lattice. The electrical sheet resistance increases in the order: graphene < P-graphene < N-graphene. This tendency is related to the density of defects evaluated from the ratio of intensities of Raman peaks, valence band XPS and NEXAFS spectroscopy data. View Full-Tex

Electron-electron interaction in carbon nanostructures

The electron-electron interaction in carbon nanostructures was studied. A new method which allows to determine the electron-electron interaction constant $\lambda_c$ from the analysis of quantum correction to the magnetic susceptibility and the magnetoresistance was developed. Three types of carbon materials: arc-produced multiwalled carbon nanotubes (arc-MWNTs), CVD-produced catalytic multiwalled carbon nanotubes (c-MWNTs) and pyrolytic carbon were used for investigation. We found that $\lambda_c$=0.2 for arc-MWNTs (before and after bromination treatment); $\lambda_c$ = 0.1 for pyrolytic graphite; $\lambda_c >$ 0 for c-MWNTs. We conclude that the curvature of graphene layers in carbon nanostructures leads to the increase of the electron-electron interaction constant $\lambda_c$.Comment: 12 pages, 18 figures, to be published in the Proceedings of the NATO Advanced Research Workshop on Electron Correlation in New Materials and Nanosystems, NATO Science Series II, Springer, 200

Electron spectroscopy of carbon materials: Experiment and theory

We present a comparative spectroscopic study of carbon as graphite, diamond and C60 using C1s K-edge electron energy-loss spectroscopy (EELS), X-ray emission spectroscopy, and theoretical modelling. The first principles calculations of these spectra are obtained in the local density approximation using a self-consistent Gaussian basis pseudo-potential method. Calculated spectra show excellent agreement with experiment and are able to discriminate not only between various carbon hybridisations but also local variation in environment. Core-hole effects on the calculated spectra are also investigated. For the first time, the EEL spectrum of carbyne is calculated

Tuning Nitrogen-Doped Carbon Electrodes via Synthesis Temperature Adjustment to Improve Sodium- and Lithium-Ion Storage

Structural imperfections, heteroatom dopants, and the interconnected pore structure of carbon materials have a huge impact on their electrochemical performance in lithium-ion and sodium-ion batteries due to the specific ion transport and the dominant storage mechanism at surface defect sites. In this work, mesopore-enriched nitrogen-doped carbon (NC) materials were produced with template-assisted chemical vapor deposition using calcium tartrate as the template precursor and acetonitrile as the carbon and nitrogen source. The chemical states of nitrogen, the volume of mesopores, and the specific surface areas of the materials were regulated by adjusting the synthesis temperature. The electrochemical testing of NC materials synthesized at 650, 750, and 850 °C revealed the best performance of the NC-650 sample, which was able to deliver 182 mA·h·g−1 in sodium-ion batteries and 1158 mA·h·g−1 in lithium-ion batteries at a current density of 0.05 A·g−1. Our study shows the role of defect sites, including carbon monovacancies and nitrogen-terminated vacancies, in the binding and accumulation of sodium. The results provide a strategy for managing the carbon structure and nitrogen states to achieve a high alkali-metal-ion storage capacity and long cycling stability, thereby facilitating the electrochemical application of NC materials

Photolysis of Fluorinated Graphites with Embedded Acetonitrile Using a White-Beam Synchrotron Radiation

Fluorinated graphitic layers with good mechanical and chemical stability, polar C–F bonds, and tunable bandgap are attractive for a variety of applications. In this work, we investigated the photolysis of fluorinated graphites with interlayer embedded acetonitrile, which is the simplest representative of the acetonitrile-containing photosensitizing family. The samples were continuously illuminated in situ with high-brightness non-monochromatized synchrotron radiation. Changes in the compositions of the samples were monitored using X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS N K-edge spectra showed that acetonitrile dissociates to form HCN and N2 molecules after exposure to the white beam for 2 s, and the latter molecules completely disappear after exposure for 200 s. The original composition of fluorinated matrices CF0.3 and CF0.5 is changed to CF0.10 and GF0.17, respectively. The highly fluorinated layers lose fluorine atoms together with carbon neighbors, creating atomic vacancies. The edges of vacancies are terminated with the nitrogen atoms and form pyridinic and pyrrolic units. Our in situ studies show that the photolysis products of acetonitrile depend on the photon irradiation duration and composition of the initial CFx matrix. The obtained results evaluate the radiation damage of the acetonitrile-intercalated fluorinated graphites and the opportunities to synthesize nitrogen-doped graphene materials

Genome resource banking in the family Felidae

Many of the extant Felidae species are endangered or vulnerable. Others being not endangered as a whole species contain endangered subspecies. Only a very few cat species, besides domestic cats, are not in the risk group. Cryopreservation of embryos and gametes is a modern approach for ex situ mammalian genetic resources conservation. Freezing of semen has been successfully applied to the domestic cat and to more than 25 wild members of this family. However, embryos/oocytes cryopreservation was successful for only a small number of felids. Domestic cat and four wild Felidae species produced offspring after cryopreservation and subsequent embryo transfer. Regarding freezing of oocytes, so far different cryopreservation methods are still being experimentally tried exclusively for domestic cat. Genome Resource Bank (GRB) containing frozen semen of Amur leopard cat, bobcat and Eurasian lynx was established at the Institute of Cytology and Genetics, Novosibirsk. As a result of this project, original methods of feline semen freezing have been developed; embryos of domestic cat have been successfully frozen as well. Approaches to freeze domestic cat’s oocytes have also been tried. During this work, we combined biological and physical methods. In particular, the process of freezing embryos and oocytes was monitored with Raman spectroscopy. Different methods of frozen-thawed spermatozoa and embryonic viability testing were used in this study, including vital staining and subsequent fluorescent and light microscopy, and heterologous in vitro fertilization

Controlling pyridinic, pyrrolic, graphitic, and molecular nitrogen in multi-wall carbon nanotubes using precursors with different N/C ratios in aerosol assisted chemical vapor deposition

Nitrogen-containing multi-wall carbon nanotubes (N-MWCNTs) were synthesized using aerosol assisted chemical vapor deposition (CVD) techniques in conjunction with benzylamine:ferrocene or acetonitrile: ferrocene mixtures. Different amounts of toluene were added to these mixtures in order to change the N/C ratio of the feedstock. X-ray photoelectron and near-edge X-ray absorption fine structure spectroscopy detected pyridinic, pyrrolic, graphitic, and molecular nitrogen forms in the N-MWCNT samples. Analysis of the spectral data indicated that whilst the nature of the nitrogen-containing precursor has little effect on the concentrations of the different forms of nitrogen in N-MWCNTs, the N/C ratio in the feedstock appeared to be the determining factor. When the N/C ratio was lower than ca. 0.01, all four forms existed in equal concentrations, for N/C ratios above 0.01, graphitic and molecular nitrogen were dominant. Furthermore, higher concentrations of pyridinic nitrogen in the outer shells and N2 molecules in the core of the as-produced N-MWCNTs suggest that the precursors were decomposed into individual atoms, which interacted with the catalyst surface to form CN and NH species or in fact diffused through the bulk of the catalyst particles. These findings are important for a better understanding of possible growth mechanisms for heteroatom-containing carbon nanotubes (CNTs) and therefore paving the way for controlling the spatial distribution of foreign elements in the CNTs using CVD processes

Edge state magnetism in zigzag-interfaced graphene via spin susceptibility measurements

Development of graphene spintronic devices relies on transforming it into a material with a spin order. Attempts to make graphene magnetic by introducing zigzag edge states have failed due to energetically unstable structure of torn zigzag edges. Here, we report on the formation of nanoridges, i.e., stable crystallographically oriented fluorine monoatomic chains, and provide experimental evidence for strongly coupled magnetic states at the graphene-fluorographene interfaces. From the first principle calculations, the spins at the localized edge states are ferromagnetically ordered within each of the zigzag interface whereas the spin interaction across a nanoridge is antiferromagnetic. Magnetic susceptibility data agree with this physical picture and exhibit behaviour typical of quantum spin-ladder system with ferromagnetic legs and antiferromagnetic rungs. The exchange coupling constant along the rungs is measured to be 450 K. The coupling is strong enough to consider graphene with fluorine nanoridges as a candidate for a room temperature spintronics material